Aqueous Emulsions Of Silicone Resins

ABSTRACT

Aqueous emulsions of a silicone resin are disclosed that provide a solid silicone resineous coating upon removing water from a film of the emulsion. The silicone resin emulsions are useful for treating various substrates for imparting water resistance/repellence and improving wear/weather protective properties. In particular, they are useful for rendering mineral-based building materials water-resistant, and also as binders in paints.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. 60/861636, filed on Nov. 29,2006.

TECHNICAL FIELD

This invention relates to aqueous emulsions of silicone resins thatprovide a solid coating upon removing water from a film of the emulsion.The silicone resin emulsions are useful for treating various substratesfor imparting water resistance/repellence and improving wear/weatherprotective properties. In particular, they are useful for renderingmineral-based building materials water-resistant while providing watervapor permeability, and also as binders in paints.

BACKGROUND

Aqueous emulsions of silicone resins are used in a variety of surfacetreatments such as additives in water based paints and coatings, as wellas in treating textile materials. Silicone resins provide protectionagainst wear and weather, increase water resistance or repellence,improve soil resistance, and allow water vapor permeation.

U.S. Pat. No. 4,582,874 discloses an aqueous emulsion of a low molecularweight silicone resin comprising by weight (a) 1-60% of a silicone resin(b) 0.1-10% of an emulsifier, and (c) water.

U.S. Pat. No. 5,443,627 teaches organopolysiloxane-alkyltrialkoxysilaneemulsions for impregnating structural fiber-reinforced cementcontaining: components (A) organopolysiloxane free from basic nitrogen,(B) an alkyltrialkoxysilane, (C) an emulsifier and (D) water.

U.S. Pat. No. 5,531,812 discloses waterproofing agents for mineralbuilding materials based on aqueous emulsions of organo-silanes and/ororganosiloxane resins containing reactive groups in which the dispersedphase has an average particle size of 0.55 to 1.1 μm and a scope ofparticle size range of less than 1.3.

U.S. Pat. No. 6,262,171 discloses an aqueous emulsion comprising thecomponents (A) organosilicone compositions selected from (A1)C₁-C₂₀-alkyl-C₂-C₆-alkoxysilanes and (A2) organopolysiloxane containingalkoxy groups, (B) organopolysiloxane containing, one or more siloxaneunits having SiC-bonded radicals containing basic nitrogen, with theproviso that the amine number of the organopolysiloxane is at least0.01, and (C) an emulsifier. The said emulsions are used for makingporous mineral building materials hydrophobic.

U.S. Pat. No. 6,294,608 discloses aqueous emulsions for imparting waterrepellency to building materials and wood. The '608 emulsions containthe components (A) organosilicon compounds which are selected from (A1)C₁-C₂₀-hydrocarbon- C₁-C₆-alkoxysilanes and (A2) branchedorganopolysiloxanes containing C₁- C₆-alkoxy groups, (B) organosiliconcompounds which are selected from (B1) C₁-C₆-alkoxysilanes containingaminoalkyl groups and (B2) branched organosiloxanes containingaminoalkyl groups and (C) an emulsifier. The aqueous emulsions aresuitable for imparting water repellency to porous mineral buildingmaterials and building coatings and to wood.

U.S. Pat. No. 4,877,654 relates to an aqueous silane emulsion comprisingof a silane which is hydrolytically stable within a certain pH range, anemulsifier and a buffering compound providing the certain pH range.

The benefits resulting from using a silicone resin emulsion may be morepronounced if the silicone resin emulsion dries to a coherent resin filmhaving good cohesion within the film and good adhesion to the substrate.Such coherent films may result from a silicone resin emulsion in whichthe emulsion droplets contain groups or functionality that react witheach other and with the substrate upon water removal. This later processis sometimes referred to as “post curing”, as opposed to “pre-curing”where the oil phase within the emulsion droplets is crosslinked prior toapplication and thus becomes non-reactive. However, silicone resinemulsions where the silicone resin contains a substantial quantity ofreactive groups, especially hydrolytically reactive groups, posesseveral challenges. For example, silicone resin emulsions have poorshelf stability due to resin hydrolysis, which often produces an alcoholthat destabilizes the emulsion. Another mechanism is resin condensationwhich results in emulsion breaking or gelling. Even when emulsionremains stable, the silicone resin in the emulsion droplet may slowlyreact such that with time, it loses some or all of the reactive groupsand as a result, the film formed from an aged emulsion has muchdiminished strength and adhesion or binding ability as compared to thatof a freshly prepared emulsion.

Another problem encountered with emulsions containing reactive siliconeresins is that the “post curing” does not reach completion after waterremoval, leaving either a liquid layer on substrate or a film which istacky or greasy. This problem may be circumvented if the substratematerial is such that it promotes post curing in the adhering film, butthis will largely limit the choice of the substrate. Alternatively, acatalyst can be incorporated in the emulsion. However the use of acatalyst in the emulsion has the disadvantage that the emulsion needs tobe used immediately after preparation, otherwise the oil phase tends topre-maturely react thus becomes hardened such that the film resultedfrom an aged emulsion loses its mechanical strength. Thus, there is aneed to identify emulsions of silicone resins that have good storagestability and provide solid, non-tacky coatings upon drying on anysurface application, and are free of catalysts.

SUMMARY

This invention relates to an aqueous emulsion comprising;

A) 1-70 weight percent of a silicone resin having an empirical formula

$R_{x}{{Si}({OZ})}_{y}(O)_{\frac{4 - x - y}{2}}$

-   -   where        -   R is a monovalent organic group having 1-30 carbon atoms,        -   Z is hydrogen or an alkyl group having 1-4 carbon atoms,        -   x has a value from 0.75 to 1.7,        -   y has a value from 0.1 to 2.0,    -   and having a viscosity of from 1 to 4000 mPa·s at 25° C.,

B) 0-40 weight percent of a hydroxy terminated polydiorganosiloxane,

C) 0.5-20% based on the weight components A) and B) of an emulsifier,

D) 0.001-5% based on the weight of the emulsion of a water soluble salt,

wherein the emulsion provides a solid coating upon removing water from afilm of the emulsion.

The silicone resin emulsions are useful for treating various substratesfor imparting water resistance/repellence and improving wear/weatherprotective properties. In particular, they are useful for renderingmineral-based building materials water-resistant, and also as binders inpaints. These silicone resin emulsion are also useful in mold releasecoatings such as those release coatings for molding polyurethane andrubber articles.

DETAILED DESCRIPTION A) The Silicone Resin

The emulsions of the present invention contain 1-70 weight percent of asilicone resin having an empirical formula;

$R_{x}{{Si}({OZ})}_{y}(O)_{\frac{4 - x - y}{2}}$

-   -   where        -   R is a monovalent organic group having 1-30 carbon atoms,        -   Z is hydrogen or an alkyl group having 1-4 carbon atoms,        -   x has a value from 0.75 to 1.7,        -   y has a value from 0.1 to 2.0,    -   and having a viscosity from 1 to 4000 mPa·s.

The silicone resins in the emulsions of the present invention areorganopolysiloxanes. Organopolysiloxanes are polymers containingsiloxane units independently selected from (R₃SiO_(0.5)), (R₂SiO),(RSiO_(1.5)), or (SiO₂) siloxy units, commonly referred to as M, D, Tand Q siloxy units respectively, where R may be any organic groupcontaining 1-30 carbon atoms. These siloxy units can be combined invarious manners to form cyclic, linear, or branched organopolysiloxanestructures. The chemical and physical properties of organopolysiloxanestructures can vary, depending on the type and number of siloxy unitspresent in the organopolysiloxane. For example, organopolysiloxanes canbe volatile or low viscosity fluids, high viscosity fluids/gums,elastomers or rubbers, and resins.

The organopolysiloxanes useful as silicone resins in the emulsions ofthe present invention may have any combination of (R₃SiO_(0.5)),(R₂SiO), (RSiO_(1.5)), or (SiO₂) siloxy units, providing theorganopolysiloxane has the empirical formula as described above and aviscosity from 1 to 4000 mPa·s at 25° C.,

-   -   alternatively from 10 to 1000 mPa·s at 25° C.,        -   or alternatively from 50 to 500 mPa·s at 25° C.

In one embodiment, the organopolysiloxane selected as the silicone resinin the emulsions of the present invention contains primarily D and Tunits. In this embodiment, the D and T siloxy besides having an Rsubstituent on the silicon atom, may also contain a hydroxy or alkoxysubstituent, designated as OZ, where Z is hydrogen or an alkyl grouphaving 1-4 carbon atoms. Although not wishing to be bound by any theory,the present inventors believe the presence of these OZ groups in theorganopolysiloxane provides reactive sites on the resin to allow it tosubsequently form a solid coating upon removal of water from theemulsion. Typically, the amount of OZ groups on the organopolysiloxanepresent as SiOZ groups is at least 10 weight % of SiOZ groups of theorganopolysiloxane, alternatively the weight % of SiOZ groups rangesfrom 10 to 40 weight percent of the organopolysiloxane. The weightpercent of SiOZ in the organopolysiloxane may be routinely determinedusing ²⁹Si NMR spectroscopy.

Alternatively, the silicone resin useful in the emulsion composition ofthe present invention has the formula:

[(R₂SiO_((2-a)/2))_(c)(OZ)_(a)][(RSiO_((3-b)/2))_((1-c))(OZ)_(b)]

where c and 1-c represent mole fractions of the siloxy units,

-   -   a is from 0 to 2,    -   b is from 0 to 2,    -   c is from 0 to 0.6,

with the proviso that a+b is from 0.10 to 2.00

-   -   R is a monovalent organic group having 1-30 carbon atoms,    -   Z is hydrogen or an alkyl group having 1-4 carbon atoms.        In this formula [(R₂SiO_((2-a)/2))_(c)(OZ)_(a)] represents D        siloxy units and [(RSiO_((3-b)/2))_((1-c)(OZ)) _(b)] represents        T siloxy units. The mole fractions of the D and T siloxy units        present in the silicone resin are indicated by the subscript “c”        and “1-c” respectively. The amount of OZ groups on each siloxy        unit may vary, as indicated by the subscripts “a” and “b”.

Alternatively, the silicone resin useful in the emulsion composition ofthe present invention may comprise the formula;

[(CH₃)₂SiO_(2/2)]_(d)[(CH₃)SiO_(3/2)]_(e)

[(CH₃)SiO_(3/2)]_(e)

[(CH₃)₂SiO_(2/2)]_(d)[(CH₃)SiO_(3/2)]_(e), or

[(CH₃)₂SiO_(2/2)]_(d)[(CH₃)SiO_(3/2)]_(e)[C₈H₁₇)₇SiO_(3/2)]_(f)

where subscripts d, e, and f are each an integer greater than zerohaving a value sufficient to provide the silicone resin with a viscosityas defined above;

alternatively d may vary from 0.4 to 1, or alternatively from 0.1 to0.3,

alternatively e may vary from 0.4 to 1, or alternatively from 0.7 to0.9,

alternatively f may vary from 0 to 0.1, or alternatively from 0.01 to0.04.

The silicone resins useful as component A) may be prepared by any knownmethod, but are typically prepared by the ring-opening reaction of acyclic siloxane followed by hydrolytic polycondensation withalkoxysilane(s) or by the hydrolytic polycondensation of alkoxysilanes.In both procedures, the ring-opening, hydrolysis and condensationreactions can be either acid or base catalyzed. These reactions are thenfollowed by catalyst neutralization, distillative removal of by-productalcohol, filtration and removal of solvent to provide the desiredproduct.

For example, an alkylfunctional silicone resin can be manufactured bypreparing a mixture of 50-90 wt % of alkyltrialkoxysilane,dialkyldialkoxysilane and/or cyclic siloxanes, dissolving the mixture inup to 50 wt % of a polar solvent. Typically, the polar solvent can be,but is not limited to, methanol, ethanol, propanol, isopropanol and/orbutanol. This mixture is then reacted with deionized water (1-20 wt %)using a suitable acid catalyst. Examples include, but are not limitedto, 0.05 wt % trifluoromethanesulfonic acid (TFMSA) or hydrochloricacid. The reaction is then followed by catalyst neutralization,distillative removal of the by-product alcohol . The mixture is thenfiltered and heated to remove solvent to yield the desiredalkylfunctional resin. Typically the alkyl group is comprised of C1-C4,the typical alkoxy group is hydroxyl, methoxy, ethoxy and/or isopropoxy.

Alternatively, silicone resins can be manufactured by preparing amixture of 50-90 wt % of alkyltrialkoxysilane, dialkyldialkoxysilaneand/or cyclic siloxanes, dissolving the mixture in up to 50 wt % of apolar solvent. Typically, the polar solvent can be, but is not limitedto, methanol, ethanol, propanol, isopropanol and/or butanol. Thismixture is then hydrolyzed with 1-20 wt % deionized water using acatalytic amount of aqueous potassium hydroxide (or another suitablebase catalyst known to those skilled in the art. Examples include, butare not limited to, sodium methylate and potassium silanolate. Thereaction is then followed by catalyst(s) neutralization, distillativeremoval of the by-product alcohol. The catalyst can be neutralized withaqueous HCl (or another suitable acid such as acetic acid). The mixtureis then filtered and solvent removed to yield the desiredalkylfunctional silicone resin. Typically the alkyl group is comprisedof C1-C4, the alkoxy group is hydroxyl, methoxy, ethoxy and/orisopropoxy.

B) The Hydroxy Terminated Polydiorganosiloxane

The emulsions of the present invention contain 0-40 weight percent of ahydroxy terminated polydiorganosiloxane. Thus, component B) is optional,but when present is any polydiorganopolysilxoxane having the generalformula;

[R₂Si(OH)O_(1/2)][R₂SiO_(2/2)]_(z)[SiR₂(OH)O_(1/2)],

where R is an organic group containing 1 to 30 carbons and z representsthe degree of polymerization and is greater than one. Typically, thehydroxy terminated polydiorganopolysiloxane is a hydroxy terminatedpolydimethylsiloxane having a degree of polymerization (z) from 1 to1000, alternatively, from 5 to 200, or alternatively from 10 to 100.

C) The Emulsifier

The emulsions of the present invention contain 0.5-20% based on theweight components A) and B) of an emulsifier. While emulsion of thepresent invention can be prepared by emulsifiers of any type, i.e.,anionic, cationic, nonionic and amphoteric, polyvinyl alcohol (PVA) isparticularly effective in achieving a film forming system. For example,the components A) and B) can be emulsified by using a nonionicsurfactant or a combination of nonionic surfactants having a combinedHLB in the range of 10-20, the resultant emulsion, upon waterevaporation, leads to a liquid or semi-solidified film on a neutralsubstrate.

Effective PVA includes those with a degree of polymerization (P_(w)) of600 to 4000, or a weight average molecular weight M_(w) of 25,000 to200,000, and with a degree of hydrolysis (from the acetate) of 70 to 98mol %, preferably 80 to 95 mol %. The use level of the active PVA rangesfrom 0.5 to 20%, alternatively from 2 to 10%, based on the total weightof components A) and B).

D) The Water Soluble Salt

The emulsions of the present invention contain 0.001-5% based on theweight of the emulsion of a water soluble salt. The water solubleorganic or inorganic salt renders the aqueous phase of the presentinvention neutral to slightly alkaline at an active level of 0.001 to 5%based on the weight of the emulsion. Examples of water soluble saltsthat can be used include alkali metal, alkaline earth metal and ammoniumsalts of carboxylic acids and phosphoric acid. Amines are alsoeffective; examples include alkylamine, diethylamine, triethylamine,ethylene diamine, monoethanolamine, diethanolamine, and triethanolamine.Sodium carbonate or sodium bicarbonate at an active use level of 0.01 to0.2% based on the weight of the emulsion are particularly effective.

Alternative to alkaline salts, organic or inorganic acid that rendersthe emulsion slightly acidic can also be incorporated which also resultsin non-greasy, tack-free films upon water removal. However, an alkalinepH of 7- 11 is preferred. More aggressive pH in the acidic or basicranges is possible so long as it does not adversely affect the stabilityof the emulsion or the resin.

Process

The sequence of combining components A), B), C), D) and water or part ofthe water is not critical. The mixture of the components is thensubjected to high shear, in devices such as a rotor stator mixer, ahomogenizer, a sonolator, a microfluidizer, a colloid mill, mixingvessels equipped with high speed spinning or with blades imparting highshear, or sonication. The water soluble salt (d) rendering the finalaqueous emulsion neutral to slightly alkaline, or acid, can be addedeither with the water phase prior to high shear, or alternatively, addedto the emulsion after it being high sheared. The later procedureprovides the emulsion with better stability.

Other additives can also be incorporated in the emulsion, such asfillers, foam control agents; anti-freeze agents and biocides.

In an alternative embodiment of the present invention, the siliconeresin emulsions are free of alkoxysilanes. As used herein, “free ofalkoxysilanes” means that alkoxysilanes are not added as an emulsioncomponent. Alkoxysilanes may be represented by the general formula; R³_(α)Si(OR⁴)_(4-α), where the subscript a is 1, 2 or 3 and R³ isindependently selected from an organic group containing 1 to 30 carbons,and R⁴ is an alkyl or carbonyl group containing one to 16 carbons. Suchalkoxysilanes are also known in the art as organofunctional silanes.Alkoxysilanes are commonly added to aqueous emulsions of silicone resinsto further react with the silicone resin and substrate. The siliconeresin emulsions of the present invention provide solid coatings uponwater evaporation from a film of the emulsion. Thus, in this embodiment,the emulsions may be considered as being “free of alkoxysilanes”, andconsequentially do not require the addition of alkoxysilanes to form asolid coating.

The present invention further provides a method for preparing a solidcoating on a surface comprising;

I) forming a film of the silicone resin emulsion compositions of thepresent invention on a surface,

II) removing water from the film to form a solid coating.

The silicone resin emulsions of the present invention characteristicallyprovide a solid silicone resin upon removing water from a film of theemulsion. Films of the emulsion may be formed by simply laying a thinlayer of less than a few millimeter of the emulsion onto a substrate andremoving the water from the film by allowing the film to dry at ambientconditions. Alternatively, the films may be heated or dried underventilation to accelerate the water removal process. Alternatively, theemulsions can be applied, such as by brushing, to a solid surface andallowed to dry at ambient conditions. The emulsions will provide aresidual solid silicone resin composition or coating. The formation ofthe solid silicone resin does not depend on the type of surface orrequire the addition of a catalyst. The emulsion can also be added to anaqueous formulation and applied to substrate.

The silicone resin emulsions of the present invention are useful fortreating various substrates for imparting water resistance/repellenceand improving wear/weather protective properties. In particular, theyare useful for rendering mineral-based building materialswater-resistant, and also as binders in paints.

Examples

These examples are intended to illustrate the invention to one ofordinary skill in the art and should not be interpreted as limiting thescope of the invention set forth in the claims. All measurements andexperiments were conducted at 23° C., unless indicated otherwise.

Materials

The silicone resins used in these Examples, labeled A, B, and C, wereprepared as described below.

Silicone Resin A

A 6,000 g batch was prepared by mixing 8,262.4 g ofmethyltrimethoxysilane, 812.8 g of octamethylcyclotetrasiloxane, 404.1 gof n-octyltriethoxysilane, and 333.3 g methanol. The mixture washydrolyzed using 4.3 g trifluoromethanesulfonic acid (TFMSA) and 1,349.8g deionized water, while heating the mixture to reflux temperature(68-70° C.) for 10 hours. The catalyst was then neutralized using 16.5 gCaCO₃. The alcohol by-product(s) and residual solvent were removed bydistillation, and the resulting composition filtered. The finalalkylfunctional silicone resin composition was analyzed and contained;16.0 mol % Me₂SiO_(2/2), 84.0 mol % RSiO_(3/2), 17.9 wt % SiOZconfirming a silicone where 1.7 mol % of the R groups are octyl radicaland the rest are methyl, Z is hydrogen or methyl, with at least 80 mol %being methyl.

Silicone Resin B

A 6,000 g batch was prepared by mixing 9,020.96 g ofmethyltrimethoxysilane, and 333.3 g methanol. The mixture was hydrolyzedusing 4.5 g trifluoromethanesulfonic acid (TFMSA) and 1,193.3 gdeionized water, while heating the mixture to reflux temperature (68-70°C.) for 10 hours. The catalyst was then neutralized using 18.0 g CaCO₃.The alcohol by-product(s) and residual solvent were removed bydistillation, and the resulting composition filtered. The finalalkylfunctional silicone resin composition was analyzed and contained;100.0 mol % RSiO_(3/2), 34.2 wt % SiOZ.

Silicone Resin C

A 6,000 g batch was prepared by mixing 6,683.3 g ofmethyltrimethoxysilane, 1605.1 g of octamethylcyclotetrasiloxane, 399.0g of n-octyltriethoxysilane, and 333.3 g methanol. The mixture washydrolyzed using 3.5 g trifluoromethanesulfonic acid (TFMSA) and 1,040.1g deionized water, while heating the mixture to reflux temperature(68-70° C.) for 10 hours. The catalyst was then neutralized using 13.4 gCaCO₃. The alcohol by-product(s) and residual solvent were removed bydistillation, and the resulting composition filtered. The finalalkylfunctional silicone resin composition was analyzed and contained;30.0 mol % Me₂SiO_(2/2), 70.0 mol % RSiO_(3/2), 18.1 wt % SiOZ.

Examples 1-3

A 12 kg of emulsion E1 was made according to the following. 50 parts ofsilicone resin A were mixed with 30 parts of a 10% aqueous solution of apolyvinylalcohol of 92% degree of hydrolysis and a molecular weight of175,000 and 20 parts of water till homogeneous. The content was thenpassed through a 2-inch pipeline Greerco™ mixer (Chemineer Corp) at 4500rpm with a back pressure of 20 psi and a pump speed of 40 Hz once. Theresultant emulsion (E1) was homogeneous and milky white.

Part of emulsion E1 was added with 0.1% sodium bicarbonate based on theweight of the emulsion and mixed to arrive at emulsion E2.

Part of emulsion E2 was then added with 0.45% additional sodiumbicarbonate and 0.25% sodium carbonate based on the weight of theemulsion and mixed to produce emulsion E3.

Particle size of the emulsions was measured using a Mastersizer™ 2000 byMalvern Instruments in the volume mode. Particle size distribution wasfound to be monomodal for all three emulsions. Diameters at 50%(Dv(0.5)) and 90% Dv(0.9)) populations are reported.

Emulsion E1, E2 and E3 was each poured into a polystyrene petri-dish anddried in air at ambient. Next day observations were made of the films.

²⁹Si NMR measurements of the resin composition in the emulsion were madewith D₂O diluted emulsions of E1 immediately after made and of E3 afterstoring it at 50° C. in a closed vial for two weeks. Methanol level inthe emulsion was measured by GC of emulsion E2 after storing at ambientfor one month and of E3 after storing at 50° C. for two weeks.

Particles size, film characteristics, pH of the emulsion, resincomposition and methanol level are summarized in Table 1. E1, E2 and E3were stable at ambient conditions for months against observable settlingor phase separation.

Examples 4-12

A 500 grams of emulsion was made according to the following. 50 parts ofa silicone resin B was mixed with 40 parts of a 10% aqueous solution ofthe same PVA as in Example 1 and 10 parts of water till homogeneous. Themixture was then sheared using a Ultra-Turrax by IKA® at 24,000 RPM for4 cycles of 30seconds each while tumbling the mixture in between cycles.The resultant emulsion (E4) is homogeneous and milky white.

Emulsion E4 was subdivided into portions of 25 g each and the portionswere added with different type of salts. The various portions (E4-E12)were poured into polystyrene petri-dishes and dried in air at ambient.Next day observations were made of the films and are summarized in Table2.

Example 13

In a stainless steel beaker was mixed 400 grams of the silicone resin Cand 150 grams of a hydroxyl terminated polydimethylsiloxane of aviscosity of 50,000 cP. To the mixture was added 330 grams of a 10%aqueous solution of the same PVA as in Example 1 and 100 grams of waterand mixed till homogeneous. The mixture was then sheared using anUltra-Turrax® by IKA® at 24,000 RPM for 4 cycles of 30 seconds eachwhile tumbling the mixture in between cycles. 20 grams of a 10% aqueoussolution of sodium carbonate was then added to the mixture and mixedtill homogeneous. The resultant emulsion (E13) was homogeneous and milkywhite. Finally, 3 grams of emulsion E13 was placed in a polystyrenepetri-dish and dried in air at ambient condition for 24 hrs resulting ina tack-free, non-greasy film.

TABLE 1 Film MeOH level Characterization pH Dv (0.5) Dv (0.9) Resinstructure measured in emulsion in emulsion Resin of E1 — — — —R_(1.158)Si(OZ)_(0.519)O_(1.162) — before where R is 98.3 mol % methyland emulsification 1.7 mol % octyl E1 (immediately Grease on top and 6.01.38 μm 4.30 μm R_(1.159)Si(OZ)_(0.498)O_(1.172) Not measured afterpreparing) bottom of film where R is 98.3 mol % methyl and 1.7 mol %octyl E2 (immediately Grease-free, tack- 8.1 1.24 μm 4.05 μm Notmeasured 0.7 wt % after preparing) free, adhering to Petri-dish E3(after stored Grease-free, tack- 9.6 1.13 μm 3.72 μmR_(1.162)Si(OZ)_(0.482)O_(1.178) 1.5 wt % at 50° C. for 2 free, adheringto where R is 98.3 mol % methyl and weeks) Petri-dish 1.7 mol % octyl

TABLE 2 Salt added to 25 g of E4 E4 E5 E6 E7 E8 E9 E10 E11 E12 NaCl, 10%soln 3 g NaHCO3, 2% soln 5 g Na2CO3, 2% soln 2.5 g NaOH, 1% soln 0.15 gTitanium(IV) 0.0125 g bis(ammonium lactato)dihydroxide, 50% solnTriethanolamine, 0.18 g 85% soln ZnSO4, 2% soln 5 g HCl, 10% soln 0.12 gpH of Emulsion 5.4 5.95 7.93 10.6 8.38 6.26 8.75 5.15 4.06 FilmCharacteristics Partially cured, Partially cured, Fully cured, Fullycured, Fully cured, Partially cured, Fully cured, Mostly Fully wet, notwet, not dry, tack- dry, tack- dry, tack- wet, not dry, tack- cured;cured, adhering to adhering to free free free adhering to free greesydry, substrate substrate substrate feel tack-free

1. An aqueous emulsion comprising; A) 1-70 weight percent of a siliconeresin having an empirical formula$R_{x}{{Si}({OZ})}_{y}(O)_{\frac{4 - x - y}{2}}$ where R is amonovalent organic group having 1-30 carbon atoms, Z is hydrogen or analkyl group having 1-4 carbon atoms, x has a value from 0.75 to 1.7, yhas a value from 0.1 to 2.0, and having a viscosity of from 1 to 4000mPa·s at 25 ° C., B) 0-40 weight percent of a hydroxy terminatedpolydiorganosiloxane, C) 0.5-20% based on the weight components A) andB) of an emulsifier, D) 0.001-5% based on the weight of the emulsion ofa water soluble salt, wherein the emulsion provides a solid coating uponremoving water from a film of the emulsion.
 2. The emulsion of claim 1wherein the emulsion composition is free of organosilanes and has a pHof 7 to
 11. 3. The emulsion of claim 1 wherein the silicone resin is anorganopolysiloxane having the formula:[R₂SiO_((2-a)/2))_(s)(OZ)_(a)][RSiO_((3-b)/2))_((1-s))(OZ)_(b)] where sand 1-s represent mole fractions of the siloxy units, s is from 0 to0.6, a is from 0 to 2, b is from 0 to 2, with the proviso that a+b isfrom 0.10 to 2.00 R is a monovalent organic group having 1-30 carbonatoms, Z is hydrogen or an alkyl group having 1-4 carbon atoms.
 4. Theemulsion of claim 3 where R is n-octyl or methyl, and Z is hydrogen ormethyl.
 5. The emulsion of claim 1 wherein B) the hydroxy terminatedpolydiorganosiloxane is present and is selected from a hydroxyterminated polydimethylsiloxane.
 6. The emulsion of claim 1 wherein C)the emulsifier is polyvinyl alcohol.
 7. The emulsion of claim 1 whereinD) the water soluble salt is an alkali metal, alkaline earth metal orammonium salt.
 8. The emulsion of claim 1 wherein D) the water solublesalt is sodium hydrogen carbonate or sodium carbonate.
 9. A method forpreparing a solid coating comprising; I) forming a film of the emulsioncomposition according to claim 1 on a surface, II) removing water fromthe film to form the solid coating.
 10. The solid coating preparedaccording to the method of claim
 9. 11. A coating composition comprisingthe emulsion composition of claim 1.